CA1297717C - Color image-forming photographic reversal element with improved interimage effects - Google Patents

Abstract

COLOR IMAGE-FORMING PHOTOGRAPHIC REVERSAL ELEMENT
WITH IMPROVED INTERIMAGE EFFECTS
Abstract of the Disclosure A reversal photographic element comprising at least two dye image-forming units, at least one unit comprising (1) a first silver halide emulsion layer spectrally sensitized to a given region of the spectrum with which is associated a dye image-forming chromogenic coupler and (2) a second silver halide emulsion layer spectrally sensitized to a different region of the spectrum than the first and containing an interimage effect-forming means such as a develop-ment inhibitor-releasing coupler, which forms either a colorless compound or a dye which does not substantially take part in the formation of the image.

Description

129~7~7 COLOR IMAGE-FORMING PHOTOGRAPHIC REVERSAL ELEMENT
WITH IMPROVED INTERIMAGE EFFECTS

The present invention is directed to the improvement of interimage effects for better eolor reproduction in revers~l photogr~phic elements for color photography. Mnre specifically, thi~Q invention i~ directed to a color image-forming photographic reversal element wlth improved interimage effects.
A photographic element for color photography usually comprise~ three silver halide photosensitive units ~enaitive to blue, green and red light respec-tively associated with yellow, magenta and cyan dye-forming compounds. Particularly useful dye-forming compounds sre color-forming couplers. With thi~ type of material, it is well known that color reproduction i9 often imperfect because of unwanted absorption of the dyes formed from the coupler~. Furthermore, dur-ing proces~ing, the development of silver halide in one of the emulsion layers may affect dye formation in an ad~acent layer according to mechanisms described hereinafter.
In element~ for color photography having three unit~ with incorporated coupler~, the three unitY respectively ~ensitive to blue, 8reen snd red llght should be protected from undesirable interac-tions during storage, exposure and development with a view to obtaining excellent color reproduction. In addition, the ~pectrel absorption of the dye formed from each incorporated color-forming coupler should be located ln an appropriate w~velength r~nge. These ~re well-known conditions to form a sRtisfactory color image.
However, it is el~o known th~t element~ for color photography exhibit various defect~ related to the difficulty of meeting these requirements.

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lZ977~7 One of the defects relsting to color image reproduction iq that the spectral-absorption charac-teriQtiC~ of the subtrActive color images obtained from color-forming couplers are not sati3factory;
i.e., the light abqorption of the dye is not confined to Q de~ired region of the spectrum and extends to other region~ of ~horter or lsnger wavelengths. Thiq defect results in reduced color satur~tion.
Another defect ariqes because, during color development of the three color ima~e-forming emul~ion layerQ, the development of an image in one of the layers may cause unwanted formation of stain in an sd~acent emulsion layer intended by definition to record another image. For example, the development of the magenta image of the green-sensitive layer may cause formation of cyan dye in the red-sensitive lsyer, but following the pattern of the magenta image. This defect result~ from the fact that the oxidation product~ of development of one of the lay-ers may diffu~e to an ad~acent layer where they would8ive rise to an unwanted coupling with the coupler present in this layer.
The above-mentioned defects cause what i5 sometime~ referred to by the term "color contamina-tion". The reaction for forming a dye image in 8given emul~ion layer affect~ the ad~acent emulsion layers whereby the latter lose their aptitude to form independent elementary images and causes in these lsyers the formation of unwanted dye image~ by color contamination.
BecauQe the problem has been acknowledged for a long time, various means have been recommended in the prior art to reduce or eliminate these color-contamination defects. For example, it h~s be~n pro-poqed to incorporate in color image-forming photo-graphic materials intermediate layers, or filter lay-~297717 er3 ~ comprising reducing compounds ~uch ~s a hydro-quinone or ~ phenol derivative, a sc~venger for oxi-dized color-developing agent, couplers forming color-less compounds, or colored couplers forming diffusi-ble dyes. However, none of theQe methods h~s beencompletely s~tisfactory.
Other methods of ~ttempting to obt~in cor-rect color reproduction consist in employing mesns having a color-corrective function. For ex~mple, a colored coupler which functions as a mask may be used as de3cribed, for example, in US P~tents 2,449,966, 2,445,170, ~,600,606 and 3,148,062 ~nd British P~tent 1,044,778. However, this method c~nnot be applied to direct-posltive color photographic materials becsu~e the unexposed area~ would ~lso be colored.
Another method employs a development inhibitor-releasing, or DIR coupler, as described by B~rr, Thirtle ~nd Vittum in Photo~. Sc. and EnR., Vol. 13, p~ges 74 to 80 and 214 to 217 (1969), and in US Patent 3,227,554. Generally, the DIR coupler releases in a layer ~n inhibitor p~ttern in accor-dQnce with the image formed in this layer, but whioh migr~tes into an ad~cent lsyer. Thus, the DIR coup-ler provideQ a correction effect ususlly designsted as ~n interimsge effect. The color-correction effect due to the DIR coupler actually results from the com-bination of several fsctors such 8S speed of the DIR-coupler resction, the sctivlty of the splittable group, the aptitude of the released inhibitor to dif-fuse in a photosensitive layer, the speed of develop-ment of each component of the photosensitive emul-sion, the coupling activity of the coupler~ present in the ssme layer or in other l~yers, etc. Msny uses of DIR couplers have been proposed in color photo-graphic material~ comprising units with ~everal emul-sion layers, e.g., a fsst lsyer snd a slow layer, as described, for example, in French Pstent 2,222,674 and US Patent 4,310,621. This correction by mean~ of DIR couplers provides sn interimage effect, but with a strong intr~layer inhlbiting effect on development, which neceqsit~tes ~ qub~t~ntial increase in silver coverage. Because the DIR coupler has a limiting effect on development, the use of such a coupler reduces contrAst and maximum density.
To reduce color contamination, fogged emul-sions may ~lso be used, particularly emulsions con-slsting of internally fogged grains or intern~llatent-image emulsions. However, these methods in which fogged silver halide emulsions are u~ed suffer from the difficulty of controlling the photographlc properties of these emulsions.
Another method consists in changing the com-position of the halides used in each layer respec-tively sensitive to blue, 8reen and red light of the color photographic material by ~djusting, for exam-ple, the proportion of iodide ions used in relation to bromide ions. This correction method is that trs-ditionally uqed for color printing photogr~phic mate-rials, and consista in causing an interimage effect during the first black-and-white development by the action of the iodide ions relea~ed from the develop-ing silver haloiodide emulsions. In such a system,interimsge effects are not desired in the color developer because of the restraining effect the iodide lons have on color development. In this method, however, the emulsion layers containing iodide ions are both causing and receiving interimage effects, which renders the control of thi~ effect more difficult.
The very multiplicity of correction methods indicstes that none of them has been fully satisfac-tory. This i~ ~lso true for other methods known to ~Z977~7 have an influence on color correction, such ~s meth-ods which vary proportions of developing Rgents, sul-fite ionQ, hydrogen ion~, buffering agents, etc.
Positive dye image-forming reversal photo-graphic material~ h~ve features different from tho~eof~negQtive dye image-forming photographic materi-~ls. NegQtive m~teri~ls ~re processed, after im~ge exposure, directly with B chromogenic developer which color-develops the neg~tive exposed are~s. On the other hand, reversal materials, ~fter imagewi~e expo-sure, ~re flrst procesQed with A black-snd-white developer which develops ~ silver im~ge in the nega-tive exposed QreQ5. Thi~ is followed by 8 revercal fogging Qtep, 8 ~econd over~ll exposure or ~ chemical fogging Atep, ~nd then development with a chromogenic developer to form ~ positive color image.
In negative dye im~ge-forming photographic materi~lQ, interim~ge effects are ~lw~ys obtained during chromogenic development. In poQitive dye imsge-forming revers~l photographic materialQ, inter-im~ge effects ~re generally obtained, QS mentioned above, during processing by the rele~se in the firQt black-Qnd-white developer of a development inhibitor a~ e function of the ~ilver development of the image-forming layers. The most generQlly used development inhibitor con3ists of iodlde ions released as a result of the development of silver haloiodide, for example, silver bromoiodide emulsion~.
To obtain interimsge effect~ in dye image-formins reversal photographic materiQls, the forma-tion of interimage effects in the second chromogenic developer by development inhibitors, ~uch ~s iodide ions or mercsptans released from incorporated DIR
couplers, W~Q generally avoided bec~use poor results Are usu~lly obt~$ned. Furthermore, when DrR couplers are incorporated in the dye image-forming layers of ~2977i7 rever~al photographlc materi~lq, they incre~se the granulsrity of the color po~ltive images obtHined.
However, the u~u81 method to obtain interim-a8e e~fects in color rever~al photographic m~terials u~ing a development inhibitor during the first black-and~white development is not satisfactory. The effect of a development inhibitor in the firQt devel-oper reqults in a lower ~ilver density with, as a consequence, the development in the chromogenic developer of a higher ~ilver den~ity and dye ima8e density.
Thus, development inhibitors produce mainly interimage effect3 ln high dye-density area~ of the po~itlve imsge, while it is often desirable to obtain interimage effect~ in low dye-density areas. Conse-quently, if the interimage effect~ are increa~ed, the sen~itivity mea~ured by neutral exposure iq lowered (whereas the ~ensitivity measured by color expo~ure remain~ ~ubstantially unchanged).
Therefore, it is desirable to provide color image-forming reversal photographic materials with improved interima8e effects.
To obviate the drawbacks ob~erved when, according to the prior art, interimage effects are produced ln the first black-and-white developer, it wa~ found, according to the present invention, that improved interim~ge effects could be obtained by releagin8 Q development inhibitor in the second chro-mogenic developer. In particular, the present inven-tion provides a lower dye image density ~nd obtains aphotngraphic ~ensitivity increased by about 0.3 log E, mea~ured by color exposure (whereas the sensi-tivity measured by neutral exposure remain3 substan-tially unchanged), by increasing the interimage effect~ due to ~ specific arr~ngement of interimage effect-forming means~

1~977~7 The present invention is based on the prem-ise that it is desirable to separate the mechanism of color image formation from the mechanism of color correction or interimage effects. Thus, according to the present invention, interimage effects are gen-erated by an emulsion layer which does not partici-pate in the formation of the image. This is in con-trast with prior-art methods in which the image-forming layers also cause interimage effects.
The invention applies particularly to print-ing materials comprised of reversal negative emul-sions.
A color image-forming silver halide reversal photographic element according to the invention com-prises at least two dye image-forming units, each unit containing at least one photosensitive silver halide layer and a dye image-former characterized in that at least one of the dye image-forming units comprises (1) a first æilver halide emulsion layer spectrally sensitized to a given region of the spectrum with which is associated a dye-forming coupler, and (2) a second silver halide emulsion layer ~pectrally sensitized to a different region of the spectrum than the first and containing an interimage effect-forming means which, upon color development, forms either a colorless compound or a dye which does not substantially take part in the formation of the image.`
According to a specifically preferred embodiment, the interimage effect-forming means is a DIR compound or coupler.
Figures 1-16 illustrate the interimage effects obtained with the invention and will be described in connection with the Examples hereinafter.

~Z97717 A three-color photographic material accord-ing to the invention has, for example, the following schematic structure:

(1) green- and/or red-sensitized + DIR coupler emulsion (2) blue-~ensitlzed emulsion + yellow-forming coupler (3) CLS interlayer 10 (4) red-sensitized emulsion + DIR coupler (5) interl~yer (6) green-sensitized emulsion + ma~ents-forming coupler (7) interlayer 15 (8) 8reen-sensitized emulsion + DIR coupler (9) interlayer (10) red-sensitized emulsion + cyan-formin8 coupler (11) polyethylene-coated paper : 20 support In this msterial, the dye image-forming units are various interlayers and lsyer~ 2, 6 and 10 senqitized to blue, green and red light end contain-ing, respectlvely, yellow, magenta and cy~n image-forming couplers. With layers 2, 6 and 10 Qre asso-ciated, respectively, layer~ 1, 4 and 8 which are the color-correcting layers Mccording to the invention.
The color-correcting layers generatlng the interimage effects comprise ~ DIR coupler snd an emulsion which is eolor-sensitized differently from that of the a~soclated image-forming emulsion which receives the interima8e effect. Thus, green- and/or red-sensitized layer 1 generates an interimage effect intended for blue-senQitized yellow image-forming layer 2. Likewise, red-sensitized layer 4 generates 12977~7 an interimage effect intended for green-sensitized magenta image-forming layer 6 or for blue-sensitized yellow image-forming layer 2.
In the above structure, the arrangement of the layers may be modified. For example, layers 4 and 6 may be interchanged or layers 8 and 10 may be interchanged.
The interlayers contain a compound for scav-enging oxidized developîng agent and, if necesQary, a means to prevent the relea~ed inhibitor from migrat-ing.
DIR couplers are well-known compounds and are described, for example, in US Patent 3,227,554.
These DIR couplers may be color-forming couplers which react with oxidized color-developing agent to form dyes and release diffusible development inhibi-tors in response to the development of silver halide. The inhibitors released can be mercaptans which diffuse to one or more dye image-forming layers and thus contribute to the formation of the de~ired interimage effects. In certain instances, DIR coup-ler~ are chosen so that, after release of the inhibi-tor, they form either a colorless compound or a com-pound which does not affect color reproduction ~e.g., a dye identical with that formed in the image layer).
Ot:her compounds capable of releasin~ in the same manner a development inhibitor by a redox mecha-nism upon color development may a~so be used.
~ s previously mentioned, when the interimage effect-forming means forms a dye during chromogenic development, this dye does not form a substantial image in comparison with the image formed by the dye-forming coupler. For this purpose and according to a particularly preferred embodiment, the interimage effect-forming mean~ is used at a coverage between 5 and 30 percent of the coverage of the dye-forming coupler.

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lZ977~7 In a color reversal photographic material corresponding to the above schematic structure, interimage effects are produced in the chromogenic developer, after the black-and-white development, in the following manner. Considering layers 8 and 10, after an imagewise neutral exposure, layer 8 would release inhibitor imagewise and would inhibit devel-opment in layer 10 accordingly. After an imagewise red exposure, layer 8 would develop completely and would release the development inhibitor nonimage-wise. Relative to the neutral exposure, this would increase the development inhibition in layer 10 in the high level of red exposure, thus increasing the effective speed of layer 10 to red light and also increasing color saturation.
Silver halide negative emulsiona of photo-graphic materials giving reversal color image~ are well known. The reversal photographic films and paperæ according to the invention are reversal films and papers with nondiffusi~le incorporated touplers, such as EktachromeTM Films and EktachromeTM
Papers of the Eastman Kodak Company.
The silver halide photosensitive emulsions of the photographic materials according to the inven-tion can contain any photosensitive silver halidesuch as silver chloride, ~ilver bromide or iodide or mixed silver halides such as silver chloroiodide, bromoiodide or chlorobromoiodide, etc.
According to an advantageous embodiment, there can be an interlayer between the image-forming layer and the interimage effect-generating layer. As mentioned above, this interlayer can contain a com-pound for scavenging oxidized developing agent.
According to various advantageous embodi-ments, the image-forming silver halide photosensitive emulsion layers are coated at a silver coverage in ;

~297717 the range of from 0.5 mg~dm2 to 20 mg/dm2, more particularly from 2 mg/dm to 10 mg/dm , ~nd the interim~ge effect-gener~ting emul~ion layers Are coated st a ~ilver coverage in the range of from 0.1 mg/dm to 10 mg/dm , more particul~rly from 0.5 mg/dm to 5 mg/dm .
According to v~rious sdvant~geous embodi-ments, the photogrsphic material of the invention is a color revers~l photogrsphic m~terial comprising st le83t one negatlve dye image-forming silver hsloio-dide photo~ensitive emulsion lsyer, which permit~
interimsge effects to be obtained by ~ction of the iodide in the first black-snd-white development step.
In the following embodiments, the yellow dye image-forming lsyer is in contact with the ~upport, which is advAntageous for the absence of mottle in reversal printing psper.
Two general structures of reversal printlng p~per were prepsred ~s follows:
Structure 1 (1) antiabr~sion l~yer (2) UV-sb~orbing compound layer (3) red-sensitized emulsion + cyHn-forming coupler (4) interlayer (~) blue-~ensitized emulsion + DIR coupler (6) lnterlsyer (7) green-sensitized emulsion + msgents-forming coup-ler (8) interlayer ~9) red-sensitized emulsion + DIR coupler (10) interlayer (11) blue-sensitized emulsion + yellow-forming coupler (12) polyethylene-coated psper ~upport ~2977~7 This structure is prepared using silver bro-moiodide emulsions having tabular grains so that the red- and green-sensitized emulsions have a low sensi-tivity to blue light. Silver bromoiodide emulsions having tabular grains are well known and are described, in particular, in U.S. Patent 4,414,310 i~sued November 8, 1983. The green-sensitized emulsion of layer 7 has a relatively high iodide content in the range from 3 to 6 percent, whereas the red-sensitized emulsion of layer 3 and the blue-sensitized emulsion of layer 11 have a low iodide content in the range from 0 to 2 percent.
In the first black-and-white development step, green-sensitized emul~ion layer 7 causes a green-on-blue interimage effect in layer 11 and a green-on-red interimage effect in layer 3. In the color-development step, layer~ 3, 7 and 11 are interimage effect-receiving layers. In the color-development step, layer 5 cause~ a blue-on-green interimage effect in layer 7 and a blue-on-red interimage effect in layer 3, while layer 9 causes a red-on-green interimage effect in layer 7 and a red-on-blue interimage effect in layer 11.
The above structure 1 illustrates another advantage of the present invention, which is the for-mation of chemical edge effects due to the diffusion of development inhibitor through the interlayer between the layer containing the DIR coupler and the image-forming layer, e.g., through interlayer 8 between layer 9 containing the DIR coupler and image-forming layer 7. Such a structure allows a higher lateral diffusion of the development inhibitor which cannot be obtained if the DIR coupler is incorporated in the image-forming layer.

12977~7 Structure 2 (1) antiQbra~ion layer (2) blue-~ensitized emul~ion + DIR coupler (3) interlayer containing ~ U~-sbsorbing compound (4) green-~en~itized emul~ion + m~genta-forming coupler (5) interlayer (6) red-sen~itized emul~ion + cyan-forming coupler (7) interlayer (8) green-sen itiæed emulsion + DIR coupler (9) interlayer (lO) blue-sensitized emul~ion ~ yellow-forming coupler (ll) polyethylene-coated paper ~upport In thi~ ~tructure, the emulsion of layer 6 has ~ high iodide content and, in the fir~t black-and-white development atep, cau~es red-on-green ~nd red-on-blue interim&ge effects, re~pectively, in layer~ 4 and lO. Layer 2 causes ~ blue-on-green interimage effect in layer 4 during the color-development step and, during thi~ ~ame pro-ces~in~ 3tep, layer 8 cau~es a green-on-blue interim~e effect in layer lO and a green-on-red interims~e effect in layer 6.
Other structures of photographic material-~according to the invention can be formed by changing the order of the layer~.
The photo~encitive emulsion~ of the photo-graphic material~ according to the lnvention may con-tain a v~riety of colloid binder~, in particular hydrophilic colloid binder~ such a~ 8elatin and other naturally occurring proteins, ~ynthetic polymer~ such as polyvinyl ~lcohol, hydrolyzed polyvlnyl acetate, a highly hydrolyzed cellulo~e ester ~uch a~ hydrolyzed cellulo~e Acetate up to a re~idual content in ~cetyl group~ of l9/lOO to 26/100, a wster-~oluble lZ97717 ethanolamine-trested cellulose ecetate, a polyacryl-amide or en imidized polyacrylamide containing 30/100 to 60~100 by weight of acrylamide and having a ~pe-cific v~scosity of 0.25 to 1.5 zein, R vinyl ~lcohol polymer containing cyanoacetyl groups such a~ vinyl alcohol snd vinyl cy~noacetate copolymer~, copolymer~
of a protein and a vinyl monomer, an ethyl acrylate, acrylic scid and ethyl methacrylate interpolymer, etc. Hydrophobic polymer~ may al~o be u~ed, in par-ticular polymers in an aqueous dispersion, e.g.,vinyl polymers in the form of lMtices, which increa~e the dimensional stability of photographic materi~
in particular polymers ~uch as described in US Pat-ent~ 3,142,586, 3,193,386, 3,062,674, 3,220,844 3,287,289 and 3,411,911.
The photosensitive emulsions of the photo-graphic materials according to the invention can be coated on a variety of support~, in particular a film of cellulose nitrate, cellulose ~cetate, polyvinyl ~cet~l, poly(ethylene terephthalate), polycarbonate, etc., Q5 well as on paper supports, e.g., those which ~re p~rtially ~cetylated or coated with bsryta or a polymer of an a-olefin such as polyethylene or pro-pylene.
The photosen~itive layers and the other lay-er~ of colloid binders of the photographic materials according to the invention can contain variou~ inor-ganic or organic hardener~, in particular, aldehydes, ketones, carboxylic-acid derivatives, ~ulfonic esters, sulfonyl halide~, vinyl sulfonic ether~, halogenated ~nd epoxy derivatives, aziridines, i~o-cyanates, carbodiimideQ, polymeric hardeners such as oxidized po]ysscch~rides, etc.
The photographic material~ according to the invention can compriqe conductive or antistAtiC l~y-ers, e.g., layers containing water-soluble salt~ such 12977~7 ~s chloride , nitrates, etc., layers of met~ls coated under reduced pressure, lQyers of ionic polymers such ~s described in US Patent~ 2,861,056 and 3,206,312 ~nd l~yers of insoluble inorganic sslts such as s described in US Patent 3,428,451.
The photographic material~ according to the invention can contain plasticizers or lubricants, e.g., polyols such ~s glycerol as described, for example, in US Patent 2,960,404, f~tty acids or fatty-~cid esters such a described in US Patents 2,588,765 ~nd 3,121,060, silicones such as described in British Patent 955,061, etc.
The photo~ensitive l~yers and the other l~y-er~ of colloid binders of the photographlc materi~ls according to the invention can contain anionic ~ur-factants such as saponin, alkylQryl-sulfon~te as described in US Patent 2,600,831, amphoteric surfac-tants such ~s deAcribed in US PHtent 3,133,816, re~c~
tion products of glycidol and an alkylphenol such 8S
de9cribed in British P3tent 1,022tB78, etc.
The photographic materials according to the invention c~n contain m~tting chemical compounds such ~g zinc oxide, tit~nium dioxide, silica, ~tarch, polymers in powder form as described in US Patents 2,922,101 Hnd 2,761,245, etc.
The photographic materiQls ~ccording to the invention c~n contain optical brightener~, in p~r-ticul~r compounds ~uch as stilbenes, triaz~nes, oxa-zoles, coumarins, etc. Water-soluble brighteners c~n be u~ed 8S described in German P~tent 972,067 and US
Patent 2,933,390, or aqueou~ brlghtener dispersions can be u~ed as described in German Patent 1,150,274, - US Patent 3,406,070, French P~tent 1,530,244, etc.
The photographic materials ~ccording to the 3s invention can cont~in light-absorbing compounds, fil-ter dye~, antihalation dyes, etc. t as described, for ~Z977~7 example, in US Patents 3,253,921, 2,274,782, 2,527,583 and 2,956,879. Mordanted dye~ can also be used as described in US Paten~ 3,282,699, etc.
The photosensitive layers and the other lay-ers of colloid binders of the photographic materialsaccording to the invention can be coated by various processes, e.g., dip coating, hopper coating, etc.
For example, processes such as described in US Pat-ents 2,681,284 and 2,761,791 and British Patent 837,095 can be used.
The following examples illustrate the inven-tion:

Example 1:
The simplified following coating was pre-pared in order to ascertain that the structure according to the invention is useful to obtain a favorable interimage effect in the case of a reversal material with negative emulsions:
(1) green-sensitized silver bromide (3 mg Ag/dm2) emulsion and gelatin ~12 mg/dm2), containing a magenta-forming coupler (3.4 mg/dm2) having the formula hereafter;
(2) layer containing a compound for scavenging oxi-dized developing agent;
(3) red-sensitized silver bromide (1 mg Ag/dm2) emul~ion and gelatin (10 mg/dm2), containing a cyan (0.6 mg/dm2) DIR coupler having the herea~ter-disclosed formula (0.6 mg/dm2).
Magenta-forming coupler Cl CH~-C - NH ~
I 11 =-~C ~ N ~ .=./C4H9 t 35Cl\ ~l, /Cl CO - CH - O - ~ ~--OH
I~t,O C2H5 Cl ~e " lZ97717 Cyan ~IR coupler OH

I~ CO(CH2 )~,_o_~ tC5~ll PMT t~5Hll PMT = phenylmercaptotetrazole radical The compound for scavenging oxidized devel-oping agent is 2,5-bis(l-methylundecyl)hydroquinone.
An identical control coating was prepared in the same manner except that it did not contain the DIR coupler and the magenta-forming layer had a sil-ver coverage of 2.5 mg/dm2.
This coating was exposed for 0.5 sec at2850K to a test object. Then it was processed according to the following sequence at 38C.

20 black-and white surface development 1 min washed 1 min color-forming development*1 min, 30 sec washed 30 sec bleach-fi~ 1 min, 30 sec 25 washed 2 min, 30 sec The surface de~eloper had the following com-poæition:

30 phenidone or 1-phenyl-3-pyrazolidone1 g ascorbic acid 10 g sodium metaborate 8H20 60 g potassium bromide 1 g water to make l Q
*The color-forming developer had the following compo-sition:

benzyl alcohol 14.6 ml ethylene glycol 14 g Deque~t 20060 from Monsanto (calcium ion complexing agent) 1.2 g Versenex 80~ from Dow Chemical (calcium ion complexing sgent) 5.0 g K2CO3 26 g KOH 1.4 g 2S3 1.57 g 3,6-dithisoct&ne-1,8-diol 0.24 g hydroxylamine sulfate 2.64 g 4-N-ethyl,N-B-(methAne~ulfonamidoethyl)-2-5.0 g methyl-~-phenylenedismine seqquiqulfate NsBr 0.4B g 15 water to make 1 Q
pH - 10.45 The re~ultq obtained are illustr~ted by the graph~ of Fig. 1, which ~how the favorable principal effect (increased ~en~itivity) for the green expo~ure and the ~econd~ry effect, also favorable, for the red expo~ure.

Example 2:
2S The following three-color material waq prepared. The amounts in parenthese~ are expresqed in mg/dm .
- gelatin overcoat ~10) - layer containing Tinuvin P0 Ciba Geigy, UV-Qbsorbing compound (5.5) and gelatin (9) Yellow Pack - blue-sensitized AgBr emul~ion layer (Ag, 3.5;
gelatin, 12) containing a yellow-forming coupler (7.8) de~cribed hereafter - interlayer containing gelatin (10.5), colloi-d~l Carey Lee ~ilver (1.7) and compound for ~cavenging oxidized developing agent (1.5) -` ~297~717 M~genta Pack - 8ree~-sensitized silver bromide layer (Ag, 3;
gelatln, B.5) containing the m~genta-forming coupler of Ex~mple l (3.4~
- interlayer contAining gelatin (6) and com-pound for scavenging oxidized developing agent (1.5) - interimage effect-causing lsyer compri~ing a red-sensiti2ed silver bromide emulsion (A~, 1; gelatin, 20) and the cyan-forming DIR
coupler (1) of Exsmple l - interlayer comprising a Lippmann emulsion (Ag, 0.5~, "grey gel" colloidal silver (Ag, 1.5), gelatin (10.5) and compound for scsv-enging oxidized developing agent (1.5) Cyan Pack - red-sensitized silver bromide layer (Ag, 3;
gelatin, 8.5) cont~ining a cyan-forming coup-ler ~3) disclo~ed hereafter - interlayer contalning gelatin (6) and com-pound for scavenging developing agent (1.5) - interlmsge effect-causing layer compri~ing a green-~en~itized silver bromide emulsion ~Ag, l; gelatin 20) and 8 DIR magenta-forming coupler (1) disclosed hereafter polyethylene-coated paper The compound fDr scavenging oxidized devel-oping agent iLs 2,5-bis(l-methylundecyl)hydroquinone.

3~

,, .

Yellow-- fQrming 0UPlQ~
CH3Cl CH3 - CCO-CH-CO-NH-~ t~Hll CH31 ~ CO(C~2)3-0~ tC5Hll I~,O

S2--., ,. 0CH2 , _, Cyan-forming coupler OH t~H
Cl~ fl~ ~NHCOCH--O--~ tC5H
15~0\ ~I C2H5 Cl 20 MagQnta DIR coupl~
PMT\ ~0 C~--C
~ N/ o I f 2H5 t~Hl 1 25\-~ ~ COCE-O~ tC H

An identical control coating was prepared except that it did not contain any DIR coupler.
The three-color materials were exposed to a color step tablet for 0.5 sec at 2850K.
The exposed materials were then processed by the procedure of Example 1 above. The favorable interimage effects obtained are shown on the graph of Figs. 2, 3 and 4. In particular, the effects on the green and red exposures are noticeable. The primary effects (improved senæitivity) are markedly favorable ~a .,~

~Z977~.7 and the import~nt secondary effects are further located in the sensitQmetric layer modulation area;
hence, they are usable.
Advanta~es The layer(s) c~using the interimage effects can have a sensitivity and a contrast different from ~he image layer, making it possible to obtain more advantageous effects. In the case of color printing paper, in which interimage effects are caused upon black-and-white development in the first developer, it is possible to add the above technique to improve color quality.
It is possible, therefore, to obtain better ad~usted and better controlled independent interimage effects by separating the interimage effect-causing means.

ExamPle 3:
This example illustrates the production of interimage effects by the action of iodide in the first black-and-white developer and the production of interimage effects in the color developer by a red-sensitized emulsion layer containing a DIR coupler.
The control coating having the following structure was prepared:

" 12977~7 1 ¦gel = 10 g/dm2 Compound L = 1.5 mg/dm I BVSME = 1.5%/gel I . . _ _ l ¦Ag = 3.5 mg/dm2 2* Imagenta-forming coupler of Ex. 1 = 3.9 mg/dm2 I gel = 15 mg/dm2 3 ¦gel = 10 mg/dm2 Compound L = 1.5 mg/dm2¦
¦ BVSME = 1.5%/gel 4 ¦gel = 12.5 mg/dm2 205 ¦gel = 10 mg/dm2 Compound L = 1.5 mg/dm2¦
BVSME = 1.5%/gel _ _ l ¦Ag = 3.5 mg/dm2 Compound L = 0.5 mg/dm2¦
25 6** ¦yellow-forming coupler o~ Ex. 2 = 8.5 mg/dm2 gel = 15 mg/dm2 / / / / / / / / / I / I I I I I I I / I I I I I
Polyethylene-coated paper support * green-sensitized single-component emulsion with tabular grains of Example 1 of U.S. Patent 4,414,310 issued November 8, 1983 containing 3 to 5% mole iodide ** blue-sensitized emulsion blend with tabular grains containing 1% mole iodide Compound L = 2.5 bis(l-methylundecyl)hydroquinone The hardening agent BVSME is bis(vinylsulfonylmethyl) ether.

A photographic m~teri~l according to the invention wa~ prep~red with ~ red-sensitized emulsion containing 8 cy~n DIR coupler:

. .
1 Igel = 10 g/dm Compound L = 1.5 mg/dm I
I BVSME = 1.5%/gel 2* lAg = 4.5 mg/dm2 gel = 15.00 mg/dm I
Imagent~-forming coupler of Ex. 1 = 3.9 mg~dm 3 Igel = 10 mg/dm Compound L = 1.5 mg/dm I
IBVSME = 1.5%/gel .

iAg = 1 mg/dm 4** icyan DIR coupler - 1.5 mg/dm Igel = 12.50 mg/dm Igel = 10 m~/dm Compound L = 1.5 mg/dm I
I ~VSME = 1.5~/gel lAg = 4 mg/dm Compound L = 0.5 m~/dm I
~*** Iyellow-forming coupler of Ex. 2 = 8.5 mg/dm I gel = 15 mg/dm / / / / / / / / / / / / / / / / / / / / / / / /
Polyethylene-coated paper support * green-sensitized single-component emulsion with tabul~r grains cont~ining 3 to 5% mole iod~de ** red-sensitized single-component emulsion with tabular gr~ins *** blue-sensitized emulsion blend with tabul~r ~_ gr~ins containing 1% mole iodide ~977~7 Cya DIR coupler ~H 0 d ~ ~--NH---f ~-~/\~ i ^
' i --(CH2)13~H3 N -- CH
T c=o CH3 S~mples of these m~terials were given step exposure~.
Five sensitometric curves were obtained, expo~ed in the following manner:
(l) Neutral, additive expo~ure, 0.5 sec, blue +
green + red Blue: wr~tten filter 98 + l.00 neutral den~ity Green: wr~tten filter 99 + O.lO neutral density Red: wratten filter 29 + 0.70 neutral density (2) Shifted neutral: additive exposure, (blue + ND =
l*) + (green + ND = l) + (red + ND = l) (3) Blue test ob~ect: Additive expoRure, blue +
(green + ND = l) + (red + ND = l) (4) Green te~t ob~ect: ~dditive expo~ure, (blue +
ND = l) + green ~ (red + ND = l) (5) Red test ob~ect: ~dditive exposure, (blue + ND =
l) + (green + ND = l) + red *MD = l meQn~: neutr~l density l.00 ProcessinR
first developer (bl~ck-and-white)l min ~t 38~C
w~hed l min, 30 sec color developer 2 min ~t 38C
35 wa3hed 30 sec bleach-fix 2 min -Flrst Bla~k-and-Whitec Developer Dequest 2006TM from Monsanto 1.41 g Versenex 80TM from Dow Chemical 8.25 g 2S3 30.0 g 5 KSCN 1.0 g KOH 9.0 g l-phenyl-4,4-dimethyl-3-pyrazolidone 1.5 g K2C03 14.0 g NaHC03 12.0 g lO hydroquinone sodium monosulfonate 23.3 g NaBr 2.4 g KI 0.008 g water to make 1 Q
pH = 9.65 The composition of the color developer i9 given in Example 1.

Blea~h-Fix B~
1.56 m solution of the ammonium salt of 115 ml ethylenediamine tetraacetic acid ferric complex sodium metabisulfite 15.4 g ammonium thiosulfate (58%) 126 ml 1,2,4-triazole-3-thiol 0,377 g water to make 1 Q
pH = 6.5 Results Magenta layçr (Fig. 5) control coating: no inter-image effect.
Fig. 6 - The sensitivity of the exposure to green is higher than neutral exposure which results in a brighter color of the reproduction of the green test object.

12977~7 Yellow layer Fig. 7 - Control co~tinF: Thi~ figure ~how~ the interimage effectq caused by iodide; the exposure to blue is more senQitive than the neutrsl one (purer reproduction of the blue test ob~ect), and the msxi-mum density is higher in the expo~ure to green than in the ~hifted neutral (reproduction of the test ob~ect more saturated in yellow).
Fig~ 8 - The interimHge effects cau~ed by the layer contAining the DIR coupler have been sdded to those cau~ed by iodide. The exposure to blue is much more sensitive thQn the neutr~l one, ~nd the m~ximum density of the red expo~ure is higher than that of the ~hifted neutral.
Example 4:
This example illu~trates the interimage effects cau~ed on a magenta lsyer by blue- and red-sen~itized associated layer~ containing a DIR coupler.
The control material having the following structure wa~ prepared:

~297717 1 Igel = 10 g/dm Compound L = 1.5 mgJdm I
I BVSME = 1.5%/gel 2* lAg = 1 mg/dm gel = 12.5 mg/dm I
.. ..

3 Igel = 10 mg/dm Compound L = 1.5 mg/dm I
I BVSME - 1.5~/gel 4** lAg - 3.5 mg/dm2 gel = 15 mg/dm2l Im~genta-forming coupler of Ex. 1 = 3.9 mg/dm l~el = 10 mg/dm Compound L = 1.5 mg/dm I
I BVSME = 1.5~/~el 1 _ l 6*** IAg = 1 mg/dm gel = 12.50 mg/dm / / / / / / / / / / / / / / / / / / / / / / / /
Polyethylene co~ted p~per ~upport * blue-~en~itized single-component emulsion with tæbular grains ** green-sensiti2ed single-component emul~ion with tabul~r græins *** red-sen~itized single-component emulsion with tabul~r grains M~terial 1 Accordin~ to the Invention It i~ identical to the control materi~l except the lsyer 6 contain~ 1.5 mg/dm of cyan DIR
coupler of Ex~mple 3.
-~2~7~17 MAterial 2 Accordin to the Invention It i~ the s~me R~ the control material, but in this c~e l~yer 2 ~ontains 1.2 mg/dm of cy~n DIR coupler of Example 3.
Muterial 3 According to the Invention LQyers 6 ~nd 2, respectively, contain 1.5 ~nd 1.2 mg/dm of cyan DIR coupler of Example 3.
Fi~. 9 - Control Material The curve representing green exposure i~
~hifted with respect to the curve of neutrsl expo-~ure, giving ~ d~rker green ob~ect. Likewi~e, the ~hifting of the curve representlng red expo~ure with respect to the curve of ~hifted neutr~l gives a less ~tur~ted red ob~ct.
Fi~. 10 - Material 1 Accordin~ to the Invention Interimage effects ~re c~uced by the red-~ensitized l~yer. The poor color rendition of the control material is improved (~ubst~ntially no effect for the expo~ure to green); a favorable effect is ob~erved even for ex~o~ure to red.
FiQ. 11 - Msterial_2 Accordin~to the Invention Interimage effects ~re caused by the blue-sen~itized lsyer. The poor rendition of green is improved and a f~vorable effect i~ noted for exposure to blue.
FiR~ 12 - M~terial 3 Accordi~8 to the Invention Interimage effects are caused by the two l~yers with DIR coupler~. Lowering of the Dmax can be compenssted for by incre~s`ing the Ag coverage of the image l~yers. F~vorable effects are produced for three-color exposures.

Ex~mPle 5:
This example is simil~r to Example 4 except that layer 2 of m~teri~l 3 cont~ins, in~tead of cyan DIR coupler of Ex~mple 3, 1.5 mg/dm of A yellow DIR coupler of the following formula:

~2977~7 Yellow DIR coypler 0 0 Cl Il 11 .
tC4H~ -G -C--C - NH~

N NH~so2-(cH2)l5-~H3 ~j, 1=o o Results:
It is noted that the control material (Fig.
13) does not exhibit interimage effects.
The materi~l uccordlng to the invention with DIR couplers (Flg. 14) retains ~ Dmax similar to the control and exhibit~ favorable interimage effects.

ExamPle 6:
This example illustr~tes the use of a com-pound cap~ble of releasing sn inhibitor by ~ redox mech~nism during color development.

.....

The control m~tericl had the following .~tructure:

5 1 Igel = 10 g/dmCompound L = 1.5 mg/dm I
IBVSME = 1.5~/gel .

2* lAg = 1 mg/dm2gel = 12.5 mg/dm I

10 Icyan DIR coupler of Example 3 = 0.8 mg/dm . _ . ._ . I

3 lgel = 10 mg/dmCompound L = 1.5 mgldm I
IBVSME = 1.5~/gel 1 _ ._ _ _ _ _l IAg = 4 mg~dmgel = 12.50 mg/dm I
4** ICompound L = 0.5 mg/dm I
Iyellow-forming coupler of Ex~mple 2 = 10 mg/dm 20 1 _ _ l / / / / / / / / / / / / / / / / / / I / / / / /
Polyethylene-coated paper support * red-sensitized single-component emulsion with t~bular 8r~in~
** blue-~en~itized e,mul~ion blend with t~bular grains Material Accordin~ to the Inventlon It 1~ identical to the control except for the layer 2 in which the cyan DIR coupler of Example 3 ha~ been replaced by 1 mg/dm of the following compound:

.

~Z9i?717 ! o \~--CH2--0--C--NH--NH--~ ~ -NH-c-cH(cH2)9-cH3 o g \.f SO

OH
Results Fi~s. 15 ~nd 16 ~how th~t the above compound cauQes interimage effects, for expo~ures to blue ~nd red, similar to those caused by the cyan DIR coupler of Example 3.
The invention has been described in detail with p~rticular reference to preferred embodiment~
thereof, but lt will be under~tood that ~ariations snd modifications c~n be effected within the spirit and scope of the invention.

Claims (16)

1. A color image-forming silver halide reversal photographic element comprising at least two dye image-forming units, each unit containing at least one photosensitive silver halide layer and a dye image-former, wherein at least one of the dye image-forming units comprises (1) a first silver halide emulsion layer spectrally sensitized to a given region of the spectrum with which is associ-ated a dye-forming coupler and (2) a second silver halide emulsion layer spectrally sensitized to a different region of the spectrum than the first and containing an interimage effect-forming means which, upon color development, forms either a colorless compound or a dye which does not substantially take part in the formation of the image.

2. The reversal photographic material of Claim 1 wherein the interimage effect-forming means is a development inhibitor-releasing compound or coupler.

3. The reversal photographic material of Claim 1 wherein the interimage effect-forming means is a compound releasing a development inhibitor, upon color development, by a redox mechanism.

4. The reversal photographic material of Claim 1 wherein the interimage effect-forming means is present at a coverage of between 5 and 30 percent of the coverage of the dye-forming coupler.

5. The reversal photographic material of Claim 1 which comprises a support coated with (a) a blue-sensitive unit containing (1) an interimage effect-causing layer comprising a green- and/or red-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler and (2) an interimage effect-receiving layer comprising a blue-sensitized silver halide photosensitive emulsion layer and a yellow-forming coupler, (b) a green-sensitive unit containing (3) a Carey Lea silver interlayer, (4) an interimage effect-causing layer comprising a red-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler, (5) an interlayer and (6) an interimage effect-receiving layer comprising a green-sensitized silver halide photosensitive emulsion layer and a magenta-forming coupler, and (c) a red-sensitive unit containing (7) an interlayer, (8) an interimage effect-causing layer comprising a green-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler, (9) an interlayer and (10) an interimage effect-receiving layer com-prising a red-sensitized silver halide photosensitive emulsion layer and a cyan-forming coupler.

6. The reversal photographic material of Claim 5 wherein layers 4 and 5 are interchanged and layers 8 and 10 are interchanged.

7. The reversal photographic material of Claim 5 wherein the interlayers contain a scavenger for oxidized development agent.

8. The reversal photographic material of Claim 5 wherein each silver halide photosensitive emulsion is a negative-working emulsion.

9. The reversal photographic material of Claim 8 wherein at least one of the dye image-forming photosensitive emulsion layers is a silver haloiodide emulsion layer.

10. The reversal photographic material of Claim 1 wherein the silver halide emulsion layer spectrally sensitized to a different region of the spectrum which contains said interimage effect-forming means forms the interimage effects during the second development which is the color development.

11. The reversal photographic material of Claim 1 which comprises a support coated with (1) an antiabrasion layer, (2) a layer containing an ultraviolet-absorbing compound, (3) a red-sensitized silver halide photosensitive emulsion layer and a cyan-forming coupler, (4) an interlayer, (5) a blue-sensitized emulsion layer and a development inhibitor-releasing coupler, (6) an interlayer, (7) a green-sensitized silver haloiodide photosensitive emulsion layer and a magenta-forming coupler, (8) an interlayer, (9) a red-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler, (10) an interlayer and (11) a blue-sensitized silver halide photosensitive emulsion layer and a yellow-forming coupler.

12. The reversal photographic material of Claim 1 which comprises a polyethylene-coated paper support coated with (1) an antiabrasion layer, (2) a blue-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler, (3) an interlayer with en ultraviolet-absorbing compound, (4) a green-sensitized silver halide photosensitive emulsion layer and a magenta-forming coupler, (5) an interlayer, (6) a red-sensitized silver haloiodide photosensitive emulsion layer and a cyan-forming coupler, (7) an interlayer, (8) a green-sensitized silver halide photosensitive emulsion layer and a development inhibitor-releasing coupler, (9) an interlayer and (10) a blue-sensitized silver halide photosensitive emulsion layer and a yellow-forming coupler.

13. A process for producing a reversal image comprising exposing the photographic element of Claim 1, developing said element in a black-and-white developer, washing said element, and then developing said element in a color developer wherein said interimage effect-forming means is released in the color development step.

14. The process of Claim 13 wherein the interimage effect-forming means is a development inhibitor-releasing compound or coupler.

15. The process of Claim 13 wherein the interimage effect-forming means is a compound releasing a development inhibitor, upon color development, by a redox mechanism.

16. The process of Claim 13 wherein the interimage effect-forming means is present at a coverage of between 5 and 30 percent of the coverage of the dye-forming coupler.